JP7060939B2 - One-component resin composition, cured product thereof, and adhesive using the same - Google Patents

Description

The present invention relates to a one-component resin composition, a cured product thereof, and an adhesive using the same, and more specifically, a cured product having good adhesiveness to metals, plastics, etc. while maintaining high strength and high heat resistance. The present invention relates to a one-component resin composition, a cured product thereof, and an adhesive using the same.

Epoxy resins are used in a wide range of industrial applications, and the performance required for epoxy resins has become more sophisticated in recent years with the development of industry. If sufficient heat resistance cannot be obtained by using an existing epoxy resin alone or in combination of multiple types, high heat resistance cyan is obtained by mixing an epoxy resin and a cyanate ester resin. Acid ester-epoxy composite resin compositions are widely used mainly for electronic component materials such as semiconductor encapsulation materials and printed wiring board applications.

Various materials such as glass, liquid crystal materials, and polarizing filters are used as materials around the display used for personal computers and smartphones, and plastics such as polycarbonate resin are used on the outside of the display. Adhesives for these materials are required to have high adhesiveness while maintaining functions such as heat resistance.

For example, Patent Document 1 proposes a composite resin composition in which an amine compound and an epoxy compound are reacted with an epoxy resin or a cyanic acid ester to combine a modified amine compound and a phenol resin. Further, Patent Document 2 proposes a fiber-reinforced composite material containing a polyether sulfone in an epoxy resin.

Japanese Unexamined Patent Publication No. 2010-006991 Japanese Unexamined Patent Publication No. 2011-016985

However, the composite resin composition proposed in Patent Document 1 can obtain a cured product having excellent storage stability and quick-curing property and excellent heat resistance, and in particular, an organic material such as polyester or polycarbonate. I was not satisfied with the adhesiveness to the product. Further, the cured product of the epoxy resin composition proposed in Patent Document 2 exhibits a high elastic modulus, high heat resistance, and high toughness, but is not satisfactory in terms of adhesiveness to metals, plastics, and the like. .. Further, when an attempt is made to further add a polyether sulfone in order to impart adhesiveness, there is a problem that the workability is deteriorated because the compatibility with the epoxy resin is poor.

Therefore, an object of the present invention is a one-component resin composition that provides a cured product having good adhesiveness to metals, plastics, etc. while maintaining high strength and high heat resistance, the cured product thereof, and adhesion using the same. To provide the agent.

As a result of diligent studies to solve the above problems, the present inventors have made an epoxy resin containing a predetermined epoxy resin, a predetermined engineering plastic, a cyanate ester and an amine-based latent curing agent, and having a predetermined structure. We have found that the above problems can be solved by adjusting the amount of a predetermined engineering plastic, and have completed the present invention.

（ここで、上記一般式（１）において、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は、それぞれ独立して、単結合、Ｏ、Ｓ、Ｃ（ＣＨ_３）_２、ＣＯ、ＣＯ_２、またはＳＯ_２を表し、Ｙ^１、Ｙ^２は、それぞれ独立して、Ｈ、Ｃｌ、またはＯＨを表し、ａは、１～１００００の整数を表す。）で表される化合物と、（Ｃ）シアン酸エステルと、（Ｄ）アミン系潜在性硬化剤と、を含む一液型樹脂組成物であって、
（Ａ１）成分の合計１００質量部に対して、（Ｂ）一般式（１）で表される化合物が、１～６０質量部であることを特徴とするものである。 That is, the one-component resin composition of the present invention comprises (A1) diglycidyl orthotoluidine and (B) the following general formula (1).

(Here, in the above general formula (1), X ¹ , X ² , X ³ , and X ⁴ are independently single-bonded, O, S, C (CH ₃ ) ₂ , CO, CO ₂ , or, respectively. Represents SO ₂ , Y ¹ and Y ² independently represent H, Cl, or OH, and a represents an integer of 1 to 10000.) And (C) cyanic acid. A one-component resin composition containing an ester and (D) an amine-based latent curing agent.
The compound represented by (B) the general formula (1) is characterized by having 1 to 60 parts by mass with respect to a total of 100 parts by mass of the component (A1).

（ここで、上記一般式（２－１）において、Ｒ^ａは２価の炭化水素基を表し、Ｒ^ｂ、Ｒ^ｃはそれぞれ独立して、非置換、または１～４個のアルキル基で置換されているフェニレン基を表す。）で表される化合物、下記一般式（２－２）、

（ここで、上記一般式（２－２）において、ｎは１～１００の整数を表し、Ｒ^ｄは水素原子、または炭素原子数が１～４のアルキル基を表す。）で表される化合物、およびこれらのプレポリマーからなる群より選ばれる少なくとも１種からなることが好ましく、下記一般式（２－３）、

（ここで、Ｒ^ｅは、単結合、メチレン基、－ＣＨ（ＣＨ_３）－、－Ｃ（ＣＨ_３）_２－、または下記一般式（３－１）～（３－８）、

（ここで、上記一般式（３－３）において、ｍは４～１２の整数を表す。）で表される何れかの官能基を表し、Ｒ^ｆ、Ｒ^ｇ、Ｒ^ｈ、Ｒ^ｉは、それぞれ独立して、水素原子、または炭素原子数が１～４のアルキル基を表す。）で表される化合物、およびこれらのプレポリマーからなる群より選ばれる少なくとも１種であることがより好ましい。さらにまた、本発明の一液型樹脂組成物においては、（Ｄ）アミン系潜在性硬化剤は、（ｄ－１）ポリアミン化合物と（ｄ－２）エポキシ化合物とを反応させてなる、分子内に活性水素を持つアミノ基を少なくとも１個有する変性アミン、および（ｄ－３）フェノール系樹脂を含有してなることが好ましい。 In the one-component resin composition of the present invention, it is preferable that the component (A1) and the component (B) are mixed and uniformly dissolved. Further, in the one-component resin composition of the present invention, the component (B) is preferably a polyether sulfone. Further, in the one-component resin composition of the present invention, the cyanic acid ester as the component (C) is described in the following general formula (2-1).

(Here, in the above general formula (2-1 ^{), Ra represents a divalent hydrocarbon group, and R b and R c are independently} substituted or substituted with 1 to 4 alkyl groups, respectively. The compound represented by (representing the phenylene group), the following general formula (2-2),

(Here, in the above general formula (2-2), n represents an integer of 1 to 100, and R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) , And at least one selected from the group consisting of these prepolymers, preferably the following general formula (2-3),

(Here, ^Re is a single bond, a methylene group, -CH (CH ₃ )-, -C (CH ₃ ) _2- , or the following general formulas (3-1) to (3-8),

(Here, in the above general formula (3-3), m represents an integer of 4 to 12), and R ^f , R ^g , R ^h , and R ⁱ represent any functional group. Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ), And at least one selected from the group consisting of these prepolymers. Furthermore, in the one-component resin composition of the present invention, the (D) amine-based latent curing agent is an intramolecular reaction of a (d-1) polyamine compound and a (d-2) epoxy compound. It preferably contains a modified amine having at least one amino group having an active hydrogen, and (d-3) a phenolic resin.

The cured product of the present invention is characterized in that the one-component resin composition of the present invention is heat-cured.

The adhesive of the present invention is characterized in that the one-component resin composition of the present invention is used.

According to the present invention, a one-component resin composition that gives a cured product having good adhesiveness to metals, plastics, etc. while maintaining high strength and high heat resistance, the cured product thereof, and an adhesive using the same. Can be provided. Since the one-component resin composition of the present invention can uniformly dissolve a specific engineering plastic in a specific glycidylamine compound, the resin material has good compatibility, and also has strength, heat resistance, and adhesiveness. Since it is excellent, it can be suitably used in the field of electronic materials such as adhesives around displays such as personal computers and smartphones, encapsulants for semiconductors, and potting agents.

Hereinafter, the one-component resin composition of the present invention will be described in detail. The one-component resin composition of the present invention comprises (A1) diglycidyl orthotoluidine, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline. It contains at least one epoxy resin, (B) a compound represented by the following general formula (1), (C) cyanate ester, and (D) a curing agent (hereinafter, simply "component (A1)" and "(A1) component, respectively". Also referred to as "(B) component", "(C) component" and "(D) component").

ここで、上記一般式（１）において、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は、それぞれ独立して、単結合、Ｏ、Ｓ、Ｃ（ＣＨ_３）_２、ＣＯ、ＣＯ_２、またはＳＯ_２を表し、Ｙ^１、Ｙ^２は、それぞれ独立して、Ｈ、Ｃｌ、またはＯＨを表し、ａは、１～１００００の整数を表す。

Here, in the above general formula (1), X ¹ , X ² , X ³ , and X ⁴ are independently single-bonded, O, S, C (CH ₃ ) ₂ , CO, CO ₂ , or SO, respectively. ₂ represents 2, Y ¹ and Y ² independently represent H, Cl, or OH, and a represents an integer of 1 to 10000.

In the one-component resin composition of the present invention, as the epoxy resin that uniformly dissolves the component (B), (A1) diglycidyl orthotoluidine or N, N-bis (2,3-epoxypropyl) -4- (2,3-Epoxy propoxy) Epoxy resin of either or both of -2-methylaniline is used. In the one-component resin composition of the present invention, the component (B) is 1 to 60 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the component (A1). Further, the component (A1) is a material that can be cured by mixing with a curing agent, heating, or the like, and also contributes to the heat resistance and adhesiveness of the cured product.

In the one-component resin composition of the present invention, an epoxy resin other than the component (A1) may be used as the component (A2). As such an epoxy resin, any compound having at least one epoxy group in the molecule can be used without particular limitation. Specifically, n-butyl glycidyl ether, C ₁₂ to C ₁₄ alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butyl phenyl glycidyl Reactive diluent with one epoxy group such as ether, t-butylphenyl glycidyl ether, glycidyl methacrylate, and tertiary carboxylic acid glycidyl ester; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butane. Reactive diluents having two epoxy groups, such as diol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether; trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, etc. , Reactive diluent having three epoxy groups; Biphenyl type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; Biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin; Dicyclo Pentaziene type epoxy resin; Naphthalene type epoxy resin; Alicyclic epoxy resin obtained from cyclohexanedimethanol, hydrogenated bisphenol A, etc .; N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxy) Propoxy) aniline and glycidylamine type epoxy resins such as N, N, N', N'-tetra (2,3-epoxypropyl) -4,4'-diaminodiphenylmethane (diglycidyl orthotoluidine, N, N-). Bis (2,3-epoxypropyl) -4- (excluding 2,3-epoxypropoxy) -2-methylaniline); phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, phenols Novolak type epoxy resin such as epoxidized product, biphenyl novolak type epoxy resin, etc. which is a condensate of and aromatic aldehyde having phenolic hydroxyl group; triphenylmethane type epoxy resin; tetraphenylethane type epoxy resin; dicyclopentadiene-phenol addition Reaction type epoxy resin; and phenol aralkyl type epoxy resin and the like can be mentioned. These compounds may be used alone or in combination of two or more.

Among the epoxy resins listed as the component (A2), novolak type epoxy resin, glycidylamine type epoxy resin (diglycidyl orthotoluidine, and N, N-bis (2,3-bis) are good in heat resistance. Epoxypropyl) -4- (excluding 2,3-epoxypropoxy) -2-methylaniline) is preferably used.

In the one-component resin composition of the present invention, the amount of the component (A2) used is the component (A1) and the component (A2) from the viewpoint of the solubility of the component (B) described later and the adhesiveness of the resin composition. It is preferably 0 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 35 to 65% by mass, based on the total mass of the above.

In the general formula (1) representing the component (B) in the one-component resin composition of the present invention, X ¹ , X ² , X ³ , and X ⁴ are independently single-bonded, O, S, and C, respectively. CH ₃ ) Represents ₂ , CO, CO ₂ , or SO ₂ , where a represents an integer from 1 to 10000. For example, if X ¹ , X ² , X ³ , and X ⁴ are all oxygen atoms, they are polyphenylene ethers, if X ¹ , X ³ are both oxygen atoms, and if X ² , and X ⁴ are both CO ₂ , polycarbonate. Will be. As described above, specific examples of the compound represented by the general formula (1) include polyphenylene ether, polycarbonate, polyethersulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyether ether ketone, and liquid crystal polymer. Be done. These polymers are so-called highly heat-resistant plastics and are a part of polymers called engineering plastics. In the one-component resin composition of the present invention, solubility in diglycidyl orthotoluidine or N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline. Are good ^points : polyethersulfone ⁽ X1, X3 ^are oxygen, X2, ^X4 _are SO2), polysulfone ⁽ X1 is SO2, X2, ^X4 _are oxygen ^{, X3} ). Is C (CH ₃ ) ₂ ), polyphenylene sulfone (X ¹ is SO ₂ , X ₂ , X ₄ is oxygen, X ³ is single bond), polyphenylene sulfide (X ¹ , X ² , X ³ , X ⁴ ). All sulfur) is preferred, and polyethersulfone is particularly preferred.

In the general formula (1) representing the component (B) in the one-component resin composition of the present invention, Y ¹ and Y ² are H, Cl, or OH, but these groups are the method for producing the component (B). It is derived from. That is, for example, as a method for producing a polyether sulfone preferably used in the present invention, dichlorodiphenyl sulfone and bisphenol S are dissolved in a high boiling point solvent such as diphenyl ether or diphenyl sulfone, and then an alkali such as potassium carbonate is used. It can be obtained by reacting with a metal salt at 140 to 340 ° C. for 1 to 20 hours. At this time, when dichlorodiphenyl sulfone is used in an excess amount of bisphenol S, the terminal of the obtained compound (that is, Y ¹ and Y ² in the general formula (1)) becomes chlorine, and bisphenol S becomes more than dichlorodiphenyl sulfone. When used in excess, the terminal of the obtained compound becomes a hydroxyl group.

Commercially available polyether sulfones include Sumika Excel PES series (manufactured by Sumitomo Chemical Co., Ltd.), PES series (manufactured by Mitsui Chemicals Co., Ltd.), Ultrazone E series (manufactured by BASF Japan Co., Ltd.), and Radel A series. (Solvay Advance and Polymers Co., Ltd.) and the like.

The amount of the component (B) used in the one-component resin composition of the present invention is the component (A1) and the component (A2) optionally used from the viewpoint of the balance between the adhesiveness and workability of the resin composition. It is 1 to 60 parts by mass, preferably 3 to 40 parts by mass, and more preferably 6 to 20 parts by mass with respect to 100 parts by mass of the total mass.

The molecular structure, molecular weight, and the like of the (C) cyanic acid ester in the one-component resin composition of the present invention are not particularly limited and can be appropriately selected from known cyanic acid esters. In the one-component resin composition of the present invention, those having at least two cyanate groups (OCN) in the molecule are particularly preferable, and are represented by the following general formulas (2-1) and (2-2), for example. Examples include compounds and these prepolymers.

ここで、上記式（２－１）におけるＲ^ａは２価の炭化水素基を表し、Ｒ^ｂおよびＲ^ｃはそれぞれ独立に、非置換、または１～４個のアルキル基で置換されたフェニレン基を表す。

Here, Ra in the above formula (2-1 ^{) represents a divalent hydrocarbon group, and R b and R c are independently} unsubstituted or substituted with 1 to 4 alkyl groups, respectively. Represents.

ここで、上記式（２－２）におけるｎは１～１００の整数を表し、Ｒ^ｄは水素原子、または炭素原子数が１～４のアルキル基である。樹脂組成物の粘度と硬化物の物性のバランスの観点から、ｎは１０～３０であることが好ましい。

Here, n in the above formula (2-2) represents an integer of 1 to 100, and R ^d is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of the balance between the viscosity of the resin composition and the physical properties of the cured product, n is preferably 10 to 30.

Among these compounds, from the viewpoint of workability, it is more preferable to use the compound represented by the general formula (2-1), and further preferably the compound represented by the following general formula (2-3). ..

ここで、Ｒ^ｅは、単結合、メチレン基、－ＣＨ（ＣＨ_３）－、－Ｃ（ＣＨ_３）_２－、または下記一般式（３－１）～（３－８）で表される何れかの官能基を表し、Ｒ^ｆ、Ｒ^ｇ、Ｒ^ｈ、Ｒ^ｉは、それぞれ独立して、水素原子、または炭素原子数が１～４のアルキル基を表す。

Here, ^Re is a single bond, a methylene group, -CH (CH ₃ )-, -C (CH ₃ ) _2- , or any of the following general formulas (3-1) to (3-8). R ^f , R ^g , R ^h , and R ⁱ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

ここで、上記式（３－３）におけるｍは４～１２の整数を表す。

Here, m in the above equation (3-3) represents an integer of 4 to 12.

The amount of (C) cyanic acid ester used in the one-component resin composition of the present invention is 10 to 1000 parts by mass with respect to 100 parts by mass of the total mass of the component (A1) and the component (A2) optionally used. It is preferably 30 to 200 parts by mass, more preferably 50 to 120 parts by mass. If it is less than 10 parts by mass, the strength of the resin composition may not be improved, and if it is more than 1000 parts by mass, the adhesiveness of the resin composition to the substrate becomes remarkable.

As the (D) amine-based latent curing agent in the one-component resin composition of the present invention, an active hydrogen-containing amine-based latent curing agent is preferable because it has excellent reactivity. Specific examples of such an active hydrogen-containing amine-based latent curing agent include an amino group having active hydrogen in a molecule formed by reacting a (d-1) polyamine compound with a (d-2) epoxy compound. Examples thereof include a latent curing agent containing at least one modified amine and (d-3) phenolic resin, a guanidine compound and the like.

Examples of the polyamine compound as the component (d-1) include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine and polyoxypropylenetriamine; isophoronediamine and mensendiamine. , Bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10 -Alicyclic polyamines such as tetraoxaspiro (5.5) undecane; m-phenylenediamine, p-phenylenediamine, tolylen-2,4-diamine, tolylen-2,6-diamine, mesitylen-2,4-diamine , Mesitylene-2,6-diamine, 3,5-diethyltrilen-2,4-diamine, 3,5-diethyltrilen-2,6-diamine and other mononuclear polyamines; biphenylenediamine, 4,4-diamino Aromatic polyamines such as diphenylmethane, 2,5-naphthylene diamine and 2,6-naphthylene diamine; imidazoles such as 2-aminopropyl imidazole and the like can be mentioned.

Among the polyamine compounds listed above, aliphatic polyamines and alicyclic polyamines are preferable from the viewpoint of the balance between curability and storage stability of the composition, and polyoxypropylene diamine, polyoxypropylene triamine, and isophorone are preferable. More preferably, it is a diamine, a bis (aminomethyl) cyclohexane, or an N-aminoethylpiperazine. These compounds may be used alone or in combination of two or more.

Examples of the epoxy compound as the component (d-2) include phenylglycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, second butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and 2-methyloctyl glycidyl ether. , Monoglycidyl ether compounds such as stearyl glycidyl ether; Monoglycidyl ester compounds such as versatic acid glycidyl ester; Polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, fluoroglucolxinol; dihydroxynaphthalene , Biphenol, Methylenebisphenol (Bisphenol F), Methylenebis (Orthocresol), Echilidenbisphenol, Isopropyridenebisphenol (Bisphenol A), Isopropyridenbis (Orthocresol), Tetrabromobisphenol A, 1,3-Bis (4-hydroxyc) Millbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, Polyglycidyl ether compounds of polynuclear polyvalent phenolic compounds such as thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovolak, terpenphenol; Polyglycidyl ethers of polyhydric alcohols such as butylene glycol, hexanediol, neopentyl glycol, dicyclopentadiene dimethanol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct. Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and glycidylmethacrylate. Epoxide compound having a glycidylamino group such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine. Vinyl Cyclohexene Diepoxide, Dicyclopentanediendiepoxide, 3,4-Epoxycyclohexylmethyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-6-Methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, Bis Epoxides of cyclic olefin compounds such as (3,4-epoxide-6-methylcyclohexylmethyl) adipates; epoxidized conjugated diene polymers such as epoxidized polybutadienes, epoxidized styrene-butadiene copolymers, triglycidyl isocyanurates and the like. Examples include heterocyclic compounds.

Among the epoxy compounds listed above, the polyglycidyl ether compound, which is a polynuclear polyhydric phenol compound, is preferable, and the diglycidyl ether of bisphenol A is particularly preferable, because it is easily available and inexpensive. These compounds may be used alone or in combination of two or more.

The amount of each component used when the (d-1) polyamine compound and the (d-2) epoxy compound were reacted to obtain a modified amine was set to 1 equivalent of the active hydrogen equivalent in the (d-1) component. In this case, the epoxy equivalent of the (d-2) epoxy compound is preferably 0.25 to 0.9 equivalents, more preferably 0.3 to 0.8 equivalents, and 0.4 to 0.6. Equivalents are particularly preferred. If it is less than 0.25 equivalents, unreacted polyamine compounds tend to remain and the storage stability of the composition tends to deteriorate, and if it is more than 0.9 equivalents, the curability of the composition is significantly lowered. Tend to do.

The phenol resin which is the component (d-3) is a phenol resin synthesized from phenols and aldehydes. Examples of the phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, and hydroquinone. , 2,2-Bis (4-hydroxyphenyl) propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, naphthol, terpenephenol, phenolated dicyclopentadiene and the like, and examples of the aldehydes include formaldehyde. ..

The reaction molar ratio of the phenols to the aldehydes is preferably 0.1 to 3.0 mol, more preferably 0.3 to 2.0 mol, and further preferably 0.3 to 2.0 mol of the aldehydes with respect to 1.0 mol of the phenols. Is 0.5 to 1.0 mol. The number average molecular weight of the obtained phenol resin is preferably 300 to 5000, more preferably 750 to 1200.

The amount of the (d-3) phenol resin used is preferably 10 to 150 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the modified amine, from the viewpoint of the balance between storage stability and curability. 80 parts by mass is more preferable, and 30 to 70 parts by mass is further preferable.

Further, as the component (D) in the present invention, latent curing comprising (d-1) an amine obtained by reacting a polyamine compound with (d-2) an epoxy compound and (d-3) a phenol resin. When the agent is used, the amount used may be 10 to 100 parts by mass with respect to 100 parts by mass of the total mass of the component (A1), the component (A2) optionally used, and the component (C). It is preferably 20 to 80 parts by mass, more preferably 20 to 80 parts by mass.

ここで、Ｒ^ｊはアミノ基、または非置換若しくはフッ素置換の炭素原子数１～１５の１価の炭化水素基、Ｒ^ｋ、Ｒ^ｌ、Ｒ^ｍは、それぞれ独立して、水素原子または炭素原子数１～４のアルキル基である。 Specific examples of the guanidine compound that can be used as the (D) amine-based latent curing agent in the one-component resin composition of the present invention are represented by the following general formulas (4-1) to (4-4). Examples thereof include compounds to be used.

Here, R ^j is an amino group, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 15 carbon atoms, and R ^k , R ^l , and R ^m are independently hydrogen atoms or carbon atoms, respectively. It is an alkyl group of the number 1 to 4.

In the one-component resin composition of the present invention, among these guanidine compounds, it is preferable to use acetoguanamine, benzoguanamine, and dicyandiamide, which have an excellent balance between stability and reactivity. These compounds may be used alone or in combination of two or more.

When the guanidine compound is used as the component (D) in the one-component resin composition of the present invention, the total amount of the component (A1), the component (A2) optionally used, and the component (C) is used. It is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass.

In the one-component resin composition of the present invention, an organic solvent can be used as a viscosity adjusting agent, if necessary. In this case, the organic solvent includes amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, and aromatics such as benzene and toluene. Examples include group hydrocarbons. In the one-component resin composition of the present invention, one or more of these solvents are mixed and 1 to 50% by mass with respect to the total mass of the one-component resin composition of the present invention. It can be blended so as to be in the range.

An inorganic filler may be added to the one-component resin composition of the present invention, if necessary. Examples of such an inorganic filler include silica such as molten silica and crystalline silica, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc molybdate, calcium carbonate, silicon nitride, silicon carbide, boron nitride, and calcium silicate. Examples thereof include powders of potassium titanate, alumina, aluminum hydroxide, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania and the like, or spherical beads thereof, glass fibers and the like. Among these, these inorganic fillers may be used alone or in combination of two or more.

The blending amount of the inorganic filler should be 5 to 90% by mass with respect to the total solid content (total mass of all components excluding volatile components such as organic solvent) of the one-component resin composition. Is preferable, and it is more preferable to make it 10 to 50% by mass. If the blending amount of the inorganic filler is less than 5% by mass, the effect of reducing the coefficient of thermal expansion of the cured product tends to be low, and if it exceeds 90% by mass, the viscosity of the epoxy resin composition increases and the workability is significantly lowered. It tends to be.

If necessary, powdered rubber may be used for the one-component resin composition of the present invention. Examples of such powdered rubber include acrylonitrile-butadiene rubber (NBR), carboxylic acid-modified NBR, hydrogenated NBR, core-shell type rubber, styrene-butadiene rubber, acrylic rubber and the like. These powdered rubbers may be used alone or in combination of two or more.

The core-shell type rubber is a rubber in which particles have a core layer and a shell layer. For example, a two-layer structure in which the outer shell layer is a glass-like polymer and the inner core layer is a rubber-like polymer, or Examples thereof include a three-layer structure in which the outer shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer. The glassy polymer is composed of, for example, a polymer of methyl methacrylate, a polymer of methyl acrylate, a polymer of styrene, etc., and the rubbery polymer layer is, for example, a butyl acrylate polymer (butyl rubber), silicone rubber, polybutadiene, etc. It is composed.

When the powdered rubber is used, the amount of the powdered rubber used is 0. 1 to 20% by mass is preferable, and 1 to 10% by mass is more preferable.

Additives other than the above-mentioned inorganic filler and powdered rubber may be used in combination with the one-component resin composition of the present invention, if necessary. Examples of the additive include non-reactive diluents (plasticizers) such as dioctylphthalate, dibutylphthalate, benzyl alcohol, and coaltal; fibrous fillers such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber; Reinforcing materials such as glass cloth, aramid cloth, carbon fiber; pigments; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N '-Β- (Aminoethyl) -γ-Aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane , Vinyl Triethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Silane coupling agents such as silane; candelilla wax, carnauba wax, wood wax, ibotarou, mitsuro, lanolin, whale wax, monttan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, Lubricants such as aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; flame retardants; antifoaming agents; rust preventives; carbon black, colloidal silica, colloidal alumina, etc. Additives can be mentioned. In the present invention, adhesive resins such as xylene resin and petroleum resin can also be used in combination.

In the one-component resin composition of the present invention, the amount used when an additive other than the above-mentioned inorganic filler and powdered rubber is used is the total solid content of the one-component resin composition (volatilization of an organic solvent or the like). The total mass of all the components excluding the components) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass.

The one-component resin composition of the present invention comprises (A1) component, optionally used (A2) component, (B) component, (C) component, (D) component, and any component added as needed. Can be produced by stirring, melting, mixing, and dispersing while heat-treating, if necessary. In this case, the apparatus used for stirring, melting, mixing, and dispersing is not particularly limited. In the one-component resin composition of the present invention, a raikai machine equipped with a stirrer and a heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill, a planetary stirrer and the like can be used. Further, these devices may be used in combination as appropriate.

The one-component resin composition of the present invention is a paint for concrete, cement, mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; Materials, adhesive film for build-up, die attachant, underfill material for flip chip mounting, grab top material, liquid encapsulant for TCP, conductive adhesive, liquid crystal sealant, coverlay for flexible substrate, resist ink, etc. Resin materials for electronic circuit boards; Semiconductor encapsulation materials; Optical materials such as optical waveguides and optical films; Resin casting materials; Adhesives; LEDs, phototransistors, photodiodes, photocouplers, CCDs, EPROMs, photosensors, etc. Various optical semiconductor devices; can be applied to various applications such as fiber-reinforced resin molded products such as CFRP. Among these applications, it is particularly preferably used in the field of electronic materials such as adhesives for materials such as metals, glass and polycarbonate used for liquid crystal displays of personal computers and smartphones, encapsulants for semiconductors, potting agents and the like. be able to.

[Production Example 1] Production of amine-based latent curing agent (EH-1) Jeffermin D-230 (polyetherpolyamine, Huntsman) was placed in a 1 L 5-port separable round bottom flask equipped with a Dimroth condenser, a stirring blade, and a nitrogen line. 230 g (manufactured by ADEKA Co., Ltd.) is charged and heated to 60 ° C., and 190 g of Adecaledin EP-491E (bisphenol F type epoxy resin, epoxy equivalent: 170 g / eq. It was added little by little so that it was kept at 110 ° C. After the addition of Adecaledin EP-4901E was completed, the temperature was raised to 140 ° C. and the reaction was carried out for 1.5 hours to obtain a modified polyamine.

MP-800K (phenol novolac type resin, softening point: 100 ° C., manufactured by Asahi Organic Materials Co., Ltd.) was charged to 100 g of the obtained modified polyamine, mixed for 30 minutes, and then 180-190 ° C., 30- The low volatile content in the system was removed at 40 mmHg over 1 hour to obtain an amine-based latent curing agent (EH-1).

[Production Example 2] Production of amine-based latent curing agent (EH-2) 130 g of N, N-dimethylaminopropylamine was charged into a 1 L 5-port separable round-bottom flask equipped with a gym funnel, a stirring blade, and a nitrogen line. It was heated to 80 ° C. While maintaining the temperature in this system at 100 to 110 ° C., ADEKA REGIN EP-4100E (bisphenol A type epoxy resin, epoxy equivalent: 170 g / eq., Manufactured by ADEKA Corporation) was added at 213 g over 30 minutes. Then, the reaction system was heated to 140 ° C. and reacted for 1.5 hours to obtain a modified polyamine.

30 g of MP-800K was added to 100 g of the obtained modified polyamine, mixed for 30 minutes, and then the low volatile components in the system were removed at 180 to 190 ° C. and 30 to 40 mmHg for 1 hour to remove the amine-based potential. A curing agent (EH-2) was obtained.

[Example 1]
Add 30 g of ADEKAREGIN EP-3980S (diglycidyl orthotoluidine, manufactured by ADEKA Corporation) and 15 g of polyether sulfone (Sumika Excel PES5003PS, Sumitomo Chemical Co., Ltd., hereinafter referred to as "PES") to a 500 mL beaker at 80 ° C. It was heated for 48 hours. After that, the mixture was stirred with a spatula, and after visually confirming that PES was uniformly dissolved, adekaresin EP-3950S (N, N-bis (2,3-epoxypropyl) -4- (2) 3-Epoxy propoxy) aniline, 70 g of ADEKA Corporation), 100 g of LECy (bisphenol E-type cyanate ester, manufactured by Ronza), 70 g of EH-1, 70 g of EH-2, and 5 at 25 ° C. Stirring was performed with a spatula for a minute. After transferring the contents to a 500 mL disposable cup, stirring was performed using a planetary stirrer to obtain a one-component resin composition of Example 1. The appearance, adhesiveness, and workability of the obtained one-component resin composition of Example 1 were evaluated according to the following methods. The evaluation results are shown in Table 1.

[Overview]
Visual confirmation was performed, and those in which the component thought to be PES was uniformly dissolved in the composition were accepted, and those in which the components were not dissolved were rejected.

[Adhesiveness]
After applying the one-component resin composition of Example 1 to a glass plate to a thickness of 100 μm, half of a PET (polyethylene terephthalate) film having a width of 5 mm is attached to the formulation, and the formulation is cured at 150 ° C. for 1 hour. I let you. Then, a 90-degree peel test was conducted using a universal bond tester 4000plus (manufactured by Nordson Advanced Technology Co., Ltd.) under a condition of a peeling speed of 0.2 mm / s. The value of adhesive strength was evaluated according to the following indexes.

A: Adhesive strength is 5 N / cm or more B: Adhesive strength is 1 N / cm or more and less than 5 N / cm C: Adhesive strength is less than 1 N / cm Was judged to be defective.

[Workability]
The viscosity of the one-component resin composition of Example 1 was measured at 25 ° C. with an E-type viscometer (cone angle: 3 degrees, cone radius: 7.7 mm, 20 rpm), and the viscosity values were measured according to the following criteria. Workability was evaluated.
A: Viscosity is 1 Pa · s or more and less than 50 Pa · s B: Viscosity is 50 Pa · s or more and less than 100 Pa · s C: Viscosity is 100 Pa · s or more In the present invention, A or B is considered to be good. C was judged to be defective.

[Examples 2 to 4, Reference Examples 1 and 2, and Comparative Examples 1 to 7]
The same operation as in Example 1 was performed except that the formulation was changed as shown in Table 1, and the one-component resin compositions of Examples 2 to 4, Reference Examples 1 and 2, and Comparative Examples 1 to 7 were performed. I got something. Each of the obtained formulations was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

＊１：Ｎ，Ｎ－ビス（２，３－エポキシプロピル)－４－（２，３－エポキシプロポキシ）－２－メチルアニリン、（株）ＡＤＥＫＡ製
＊２：ビスフェノールＡ型エポキシ樹脂、（株）ＡＤＥＫＡ製

* 1: N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline, manufactured by ADEKA Corporation * 2: Bisphenol A type epoxy resin, Co., Ltd. Made by ADEKA

As shown in the results of Table 1, it was found that in the resin composition of the present invention, the adhesion between PET and glass was good, the viscosity of the formulation was kept low, and the workability was also good. In Comparative Examples 1 and 5 to 7 in which the resin composition of the present invention was not used, the adhesiveness was poor and satisfactory results could not be obtained, and in Comparative Examples 2 to 4, PES was uniformly dissolved. I couldn't make it, and I couldn't make a subsequent evaluation.

Claims (8)

(A1) Diglycidyl orthotoluidine and (B) The following general formula (1),

(Here, in the above general formula (1), X ¹ , X ² , X ³ , and X ⁴ are independently single-bonded, O, S, C (CH ₃ ) ₂ , CO, CO ₂ , or, respectively. Represents SO ₂ , Y ¹ and Y ² independently represent H, Cl, or OH, and a represents an integer of 1 to 10000.) And (C) cyanic acid. A one-component resin composition containing an ester and (D) an amine-based latent curing agent.
(A1) A one-component resin composition, wherein the compound represented by the general formula (1) is 1 to 60 parts by mass with respect to a total of 100 parts by mass of the components. The one-component resin composition according to claim 1, wherein the component (A1) and the component (B) are mixed and uniformly dissolved. (B) The one-component resin composition according to claim 1 or 2, wherein the component is a polyether sulfone. The cyanic acid ester, which is the component (C), has the following general formula (2-1),

(Here, in the above general formula (2-1 ^{), Ra represents a divalent hydrocarbon group, and R b and R c are independently} substituted with an unsubstituted or 1 to 4 alkyl groups, respectively. The compound represented by (representing the phenylene group), the following general formula (2-2),

(Here, in the above general formula (2-2), n represents an integer of 1 to 100, and R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) , And the one-component resin composition according to any one of claims 1 to 3, which comprises at least one selected from the group consisting of these prepolymers. The cyanic acid ester, which is the component (C), has the following general formula (2-3),

(Here, ^Re is a single bond, a methylene group, -CH (CH ₃ )-, -C (CH ₃ ) _2- , or the following general formulas (3-1) to (3-8),

(Here, in the above general formula (3-3), m represents an integer of 4 to 12), and R ^f , R ^g , R ^h , and R ⁱ represent any functional group. Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ), And the one-component resin composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of the compound represented by these and a prepolymer thereof. A modified amine having at least one amino group having active hydrogen in the molecule, which is formed by reacting (d-1) a polyamine compound with (d-2) an epoxy compound by (D) an amine-based latent curing agent. The one-component resin composition according to any one of claims 1 to 5, which comprises (d-3) a phenolic resin. A cured product, wherein the one-component resin composition according to any one of claims 1 to 6 is heat-cured. An adhesive comprising the one-component resin composition according to any one of claims 1 to 6.